Table 1.
Recovery Following Addition of Known Amounts of Various Compounds to liver No. o f
Compound
Tesfs
Added
Phenothiazine Phenothiazone Thionol Phenothiazine-5sulfoxide
5 5 5 5
8-20
Ronge, P.P.M. Recovered
8-18.6 6.5-17.6 1.8- 7 . 5 3.2-13.5
7-1 8 2- 9 4-1 5
Ronge Recovery,
%
97-101.5 87.2 -100 83.5 - 93 8 6 . 5 - 94
orange-pink solution had an absorption band a t 445 mp and was unstable; however, addition of one drop of ferric chloride solution produced a stable color with a maximum absorption a t 520 mp.
Literature Cited (1) Barnett, E. de B.; Smiles, S., J . Chem. SUC.95. 1233 11909).
sented in Table I. Known amounts also were added as single tests to kidney, bile, intestinal contents, and two samples of commercial feed stuffs. I n each case, the recovery of the individual compound was within the ranges reported for that compound in Table I, column 5. The quantitative determination of phenothiazine and phenothiazone was based on their conversion to the ambercolored .V-nitroso derivatives. This was carried out by treating the phenothiazine eluate directly with nitrous acid and in the case of phenothiazone, by first
reducing the eluate and then treating it with nitrous acid. I n both instances the colors were stable for at least 1 hour. I n the case of thionol, advantage was taken of its intense blue color in alkaline solution which had a strong absorption band a t 590 mp, possibly the spectrum of the phenolate ion ( 3 ) . The color was not stable at high concentrations and so was read as soon as possible after addition of the alkaline buffer. Phenothiazine-5-oxide is converted to the sulfonium salt ( I , 2, 5) when it is dissolved in strong acid. T h e resulting
PESTICIDES A N D F O O D F L A V O R
(2) Ibid.:97,186 (1910). ’ (3) Collier, H. B., Allen, D. E., Swales, W. E.. Can. J . Reseurch ZlD, 151 (1943).’ (4) Granick, S., Michaelis, L., J . Am. Chem. Svc. 69, 2983 (1947). (3) Hilditch, T. P., Smiles, S., J . Chem. Sac. 101, 2294 (1912). (6) Houston, D. F., Kester, E. B., D e Eds, F., J . Am. Chem. Svc. 71, 3816 (1949). (7) Pummerer, R., Gassner, S., Ber. 46, 2310 (1913). Rpcrioed for reoiew April 14, 1960. Accepted ;Yoorember 7, 7960.
ELIZABETH F. MURPHY University of Maine, Orono, Maine ALICE M. BRIANT N e w York State College of Home Economics, Ithaca, N. Y. MARY 1. DODDS Pennsylvania State University, University Park, Pa.
Effect of Insecticides and Fungicides on the Flavor Quality of Fruits and Vegetables
1. S. FAGERSON University of Massachusetts, Amherst, Mass. MARY E. KIRKPATRICK Human Nutrition Research Division, U. S. Department of Agriculture, Beltsville, Md.
R. C. WllEY University of Maryland, College Park, Md.
A
S O R T H E A S T REGIONAL P R O J E C T
(SE-
15) was activated in July 1954 to determine the effects of pesticides on the quality of fruits and vegetables by means of organoleptic tests. Its primary concern was to uncover any association of poor flavor quality or off-flavor with pesticidal treatments. The first task of the committee was to determine the extent of agreement on sample ratings among panels in different laboratories through exchange of samples. A second objective was the development of a scoring technique which would quickly, economically, and precisely evaluate the off-flavor hazard in the use of pesticides.
214
Preliminary Procedure
to pesticides. Three examples illustrate this confounding.
I n 1954, a lack of uniform test material hampered the work of the committee because the project was activated too late to plant and treat crops specifically for the study. The use of crops designed for other purposes forcefully pointed to the necessity of an adequate supply of samples as uniform as is possible with biological material and controlled in every respect except for the variable under study. Some of the first year’s experiments were confounded by extraneous influences whereby significantly different results could erroneously be attributed
Incomplete sealing of a few cans of snap beans resulted in flat-sour development, thereby nullifying an experiment. The inclusion of some immature squash (to obtain sufficient control sample) resulted in overprocessing at the same time-temperatures that were optimum for mature squash. The resulting scorched flavor confounded the results of the study. Apple juices from methoxychlortreated trees were significantly lowerscored and in some cases rated as offflavor by nearly all of the participating laboratories. I t was known that the methoxychlor-treated trees were heavily
AGRICULTURAL AND FOOD CHEMISTRY
During 6 years, seven experiment stations and the Bureau of Human Nutrition, U. S. Department of Agriculture, tested by organoleptic methods the effects of pesticides on the flavor of 20 vegetables and three fruits. Common samples were exchanged and evaluated by the cooperating agencies, using a method developed b y the group. Some pesticides were tested enough times ( 1 1 to 68 tests) to derive a picture of the distribution of flavor effects in terms of a control sample-Le., better, equal, poorer, slight, and definite offflavor. Five single insecticides and one fungicide were associated with a notable degree of poor flavor quality. Six combinations of pesticides had adverse effects on flavor. Some of these seemed to be related to specific components of the multiple treatments, while others were ascribed to interaction. No ill effect on flavor quality was noted in association with ten insecticides, three fungicides on potatoes, and three fungicides on apples.
Inst~il~t::-s:
1
Check t;e
c o l m where y-u t h i n i each ssxple belongs
I
1
I
5 6
1
1 1:St
;r
t ~ . ~ g : s ~ t e W-
!
!
,
I
~ S :
?i;ze~
Fx~Tu,~
8':iiit ZaTthy
'ledlcinal 'etallic :bty
?la3
:~ly ?ItTid
Fwkery 'axcld
Salty SCLV
Spicy sueet
Umdy
Figure 1 .
NE-15 score sheet for flavor evaluation
Values assigned t o each category a r e given in parentheses below columns. The values a r e used for mean score calculations.
damaged by mites and the apples: therefore, less ripe. Thus a maturity difference was associated Lvith the pesticide treatment. I n consequence, the results from that treatment had to be omitted. These experiences emphasize the need for the quality investigator to have a completely detailed history of the samples from planting through all stages of growth, harvest. storage, and processing in order to evaluate cause with effect intelligently. A four-point scale was used in 1954. This was built around a conception of average flavor: 4> better than average; 3, average; 2 and 1, slight and definite degrees of off-flavor. The method \vas considered by the judges to be wanting in two respects: a need for a labeled standard sample (untreated or previously shown to be of good quality) to give them a common reference point and a fifth scale point to indicate poorer than standard but not necessarily off-flavor.
Accepted Procedure
I n 1955, a five-point scale with a labeled standard \\as adopted (Figure 1). T h e samples were judged in relation to a coded or "blind" reference sample, which \vas always included as a n unknown. Scores of + 2 to -2 were assigned for variance analysis, so that a final minus score indicated off-flavor, with its m a q i t u d e showing the degree of off-flavor (2. 3 ) . \Yith this method, excellent agreement was obtained among several laboratories ivith panels differing in size and composition ( 3 ) . A list of suggested words \vas appended to the score sheet for the judges to use in identifying the off-flavor (if any), but the result was meaningless because of disagreement on the connotation of descriptive terms. Good correlations were obtained only in a general breakdown between words conveying "pleasant" LS. "unpleasant" taste sensations.
Semantic agreement would undoubtedly be possible with intensive panel training on the the identification of individual flavors. This would presuppose the knoivledge by the investigator of the specific off-flavor developed in the final product form (which could be a metabolite of entirely different flavor than the original additive) and be extremely timeconsuming with panels having as many as 40 judges. I n a few instances, other organoleptic techniques were used : Ranking and paired comparisons were used for a number of tests. These methods d o not lend themselves to an interpretation of off-flavor and must result only in "significantly better or poorer" than the standard. A five-point scoring technique \vas used in some tests by the Human Yutrition Research Division, in which 5 indicared no off-flavor and 4 to 1 were degrees of off-flavor. T h e panels varied in number from five trained people to 40 or more. All laboratories selected judges who had demonstrated taste acuity in previous studies. I n general, each unir in the tables represents a mean value from a minimum of 40 judgments (judge X replication). I n relatively fe\v instances the value was derived from 20 judgments (5 judges x 4 replications). Most of the results from 1935 through 1960 are based on the 1955 NE-15 method (Figure 1) ivherein t\vo criteria had to be satisfied in order to label a sample "off-flavor": (A) I t must be significantly ( P = 0.05) lower-scored than the coded standard and (B) it must be associated with a minus score. Results I n 1960, the project was terminated and a list of all of the tested pesticides was prepared. The resulting data are shown in the tables. Table I demonstrates the effects of insecticides on the flavor of fruits and vegetables when a single insecticide was the only variable. Table I1 lists the observed influences of single fungicides on flavor. Table I11 shows the effects of multiple pesticides on flavor-
VOL. 9, NO. 3, M A Y - J U N E
1961
215
Table 1.
Flavor Evaluations of Crops Treated with Single Insecticides Flavor Compared to Sfondordd Total l b . AcfualC Acre
loco-
Insecticide
Aldrin
Product
Carrot, canned, stored, frozen, cooked Potato, new. stcred. baked Residue Carrot, cooked Turnip, coohed
Amer. Cyan. 24055 Broccoli, frozen Bacillus thuringiensis Cabbage, raw, cooked BHC Bean, snap, canned Peach, frozen, canned Residue Carrot, cooked Corn, frozen Turnip, cooked Chlordan
Cabbage, raw, cooked Carrot. raw, cooked, canned, frozen Parsnip, cooked Potato, new. stored. baked Turnip, cooked Residue Carrot, cooked Turnip, cooked
fi0na.h
Off-
No. of Crop Years
Jested byb
Beffer
2
DE
2l/2 and 3 . 0
3
EHK
E
2l/2 and 3 . 0
3
E
B B
4 yr. 3 yr.
1
C C
= =
190; test yr. = 0 65; test yr. = 0
1
F E
2.0 9.0
1 1
FK E
F F
' / i and 3 / 4 0.25/100J (1 and 2 app.)
1 1
DF EFHK
B K B
4 yr. = 190; test yr. = 0 0.125 to ',I?: test yr. = 0 3 yr. = 130; test yr. = 0
1 1 1
C K C
E BDE
9 . 0 to 4 0 . 4
5 . 0 to 2 0 . 0
2 5
E CDE
B E B
5 . 0 and 1 0 . 0 8 . 0 and 1 0 . 0 5 . 0 and 10 0
1 3 1
C E C
B B
4 y r . = 190: test yr. = 0 3 yr. = 130: test yr. = 0
1 1
C C
Peach, fresh. canned. stored Bean, snap, canned Bean, Lima. canned Cabbage, raw, cooked Carrot, frozen, cooked Cucumber, raw Potato, new, stored, baked Residue Carrot, cooked
B F F E ED E EF
O,0225/tree 1 . O and 2 . 0 5 . 0 and 1 0 . 0 9.0 10.0 Reg. 4 . 0 ; pur. 1 6 . 0 1 0 . 0 and 20.0
(I),
2
B
4 yr.
=
190; test yr. = 0
3
__
1
C
-
Dibrom (R.E. 4355)
Dieldrin
Dilan
Bean. snap. canned Bean. Lima, canned Broccoli. frozen Cabbage, cooked Egg plant. cooked Potato, cooked Tomato juice, canned
F F F F F F F
1 . 0 and 7 . 0 1.0 21/4 2.0 2.0
2
Potato, new. baked Squash, canned Sweet potato. baked Turnip, cooked Residue Carrot, cooked Turnip, cooked
E D B D
Bean, snap, canned Potato, cooked Residue Turnip, cooked
2 0 23/4 and 7 . 0 0 . 7 and 1.575 1. o
1 2 1 1
F F E CFK
1 . 0 to 4 . 0
2 1 1 1 1 1
FK F FK F F F F
21/? 1. o 11/2 and 2'/2 0.39 to 6 . 0
1 1 1 2
E D C D
B B
4 y r . = 190; test yr. = 0 3 yr. = 65; test yr. = 0
1 1
C C
F F
' / z to
2.0
4 1
DEFHK F
B
3 yr. = 130; test yr. = 0
1
C
ll/?
11/!
1
1
Endrin
216
Bean: snap, canned Bean: Lima, canned
F F
1. o 5.0
1 1
FK FK
Cantaloup, raw Carrot, canned Cucumber, raw Potato, new, baked Squash, canned Sweet potato, baked Watermelon, raw Residue Carrot, canned
D D D E D B D
2112
3.0 to 21/2 21/a 3 / 4 tc 2 . 0 2'12
2.0
1 2 2 1 3 1 1
D DEHK D E DEFK C D
1 yr. = 3 . 0 ; test yr. = 0
1
DE
D
3/4
AGRICULTURAL A N D FOOD CHEMISTRY
1
5
(2)
6 4 9
5 1
(1 ( 12 21 3 4 4 2 1
-
1
2
1
2
1 1
6
(1, 19
-
1
2 3 2 5 12 5 1 3 1 1 1 1 13 1
1
1
1
3 6 (1
__
1 1
1
Dylox
(1)
2 4 2
1
F F E B
7 2 2 4
-
5
Bean, snap: canned Broccoli, frozen Potato, stored, baked Tomato juice, canned
1
3 (4)
(7)
2
Diazinon
( 1 )
2
CH FK TK E E E CEF
1 1 1 1 3 1
3
4
3
Chlorthion DDT
Poorer flavor Number o f Jests Equal
(1) 10 19 1
(1) 20 2 1 3
1 1
1 4
3
3 1
2
6
1
1 1
(2)
(2 3
Flavor Compared t o Standardd
Acre
N o . of Crop Years
3 yr. = 6 5 . 0 ; test yr. = 0
1
Total Lb. Actualc
locaInsecticide
Product
Turnip, cooked Ethion (1240)
Guthion Heptachlor
Isodrin Kepone Korlon (Dow Et 14) Lead arsenate
Bean: snap, canned Bean, Lima. canned Egg plant. cooked Potato. cooked Tomato juice, canned Peach, fresh, canned Broccoli, fresh, frozen Cantaloup. raw Carrot. raw, cooked, frozen, canned Corn, cooked Parsnip, cooked Potato, cooked Squash. cooked Sweet potato, baked Tomato juice. canned Turnip, cooked It'atermelon, raw Residue Corn. frozen Turnip, cooked
tiona,b
B
OffTested bYh
C
F F F F F
and 2 . 0 2l/2 and 3 . 0 4'/2 4'/4 41/4
2 2
1
FK FK F F F
B FM D BDE
0.015 lb./tree 1 3 1 ~to 4 . 0 4'/2 2'/? to 6 0
1 2 1 5
CH FM D CEHK
M B BEM D B B BD D
2 . 0 and 4 . 0 3 . 0 and 6 . 0 2 . 0 to 6 . 0 3.0 2'/? 1.0 0 . 6 to 6 . 0 4.5
1 1 3 1 1 1 3 1
M C CEM D C CFK Cil D
K B
to 1 . O ; test yr. = 0 3 yr. = 130; test yr. = 0
1 1
K C
1
1
Better
Equal Poorer ~- Number of tests
3 1 -
1 1
i
6
1
4
2 1
14 1
(4) __ 7
3 yr. = 65; test yr. = 0 1. o
1 1
3/4
1
C F CFK
1
Apple juice. frozen Apple sauce, canned
A A
3,0/'100f 3.0/'100/ (4 and 5 app.)
2 1
DEF DEFHK
2 -
Bean, snap, canned Cantaloup. raw Potato, new, stored, baked
F BD E E D D
0 . 2 and 0 . 6 l ' / a and 1 . 4 "4 to 3'/r and 13/4 13/aand 5>/2
1 2 2 1 2 2
DF CD E E DFK D
1 1
1 1
4 yr. = 190; test yr. = 0
1
C
__
-
(1 1
1 2
Applesauce, canned Broccoli, frozen Cabbage, cooked Cantaloup, raw Cucumber, raw Residue Carrot, cooked
3.0/100f 1'/4 to 33/r 4.0 2'12 to 133/4 9.0 5 . 0 to 1 0 . 0 8 , O and 1 0 . 0 9.0 l l / ,A . to 5 . 0 8'/? and 133/4 4 . 0 to 7 . 0 1 . O and 8l/2 7 0 and 8 . 0
1 1 4 1 2 1 3 2 1 1 2 3 1 3
DEFHK F DEFHK F F E D DE F C F DFK CFK D
A F F D E
3.0/100/ and 1 1 / 2 1. o 9 . 0 and 12'/2 8.0
1 1 1 2 1
K F F D E
B
4 yr. = 190; test yr. = 0
1
C
11/4
1
1
2 1
5
Phosdrin Ryania
Bean, snap, canned Broccoli, frozen Bean, snap, canned Broccoli, frozen Potato. cooked
F F F F F
Broccoli, frozen Apple juice, frozen
F A
1. o 11 . O and 1 4 . 0
1
F
to 2 . 0 3.0
2 1 2 1
F F F F
'/z and 51/2
1
6.0/100f
2
F DEF
'/2 '/2
4 3 7 2 2 1
-~
7 7 2 21 1 4 2 2 2 1 3 2 1 2 __2 52
4 _. 4
1 1 3 2 2
_._
1 1
(1)
9 2
2
3
1
1
2 1 1 10 1
1
2 1
1
1 1 -
1
Parathion Perthane Phorate (Thimet)
48 1
B F B
2
Methoxychlor (marlate)
(5) -
D
A F F F F E D DE F B F D BF D
1
10
1
Apple sauce. canned Asparagus. canned, frozen Bean, snap. canned Bean. Lima. canned Broccoli. frozen Cabbage, raw. cooked Cantaloup, raw Cucumber, raw Egg plant, cooked Mushroom, canned Potato, cooked Squash, cooked, canned Tomato juice. canned IYatermelon. raw
-
1
4
3.0
B
5
5
D
93/4 3/4
-
1 1 10 5
Turnip, cooked Residue Turnip. cooked Cabbage, cooked Toniato juice, canned
Squash, cooked, canned IYatermelon, raw Residue Carrot, cooked Malathion
15 5 2 1
2
Lindane
(1) -
flavor
1
2 2 1 2 3 1 6 2
_-
2
2
1 1 -
1
8
(Continued on page 218)
VOL. 9
NO. 3, M A Y - J U N E
1961
217
Table I.
Flavor Evaluations of Crops Treated with Single Insecticides (continued) Flavor Compared fo Standardd Total lb. ActualC
locaInsecticide
Sevin
Product
Acre
tionas*
No. o f
Off-
Crop rears
Tested
by
Better
Equal Poorer Number o f Tests
Bean, snap, canned Bean? Lima, canned Egg plant, cooked Potato, cooked Tomato juice, canned
F F F F F
1 . 0 to 4 . 0 4 3 j 4to 1 0 . 0 7.0 6'/2 6'/r
2 2 1 1 1
FK FK F F F
Residue Carrot, cooked
B
4 yr.
1
C
(1)
Bean, snap: canned Bean, Lima, canned Broccoli, frozen Cabbage, cooked Egg plant, cooked Peas, canned Potato, cooked Tomato juice, canned Strawberry, raw
F F F F F F F F E
1 . 0 and 2 . 0 3 . 0 and 5 . 0
2 2 2
FK FK FK F F FK F F E
5 2 4 1 1 1
flavor
8 7
1 1 1 18
TDE
Thiodan
=
190; test yr. = 0
1 1 1 3 1
1
5 1 1 21
Toxaphene
Broccoli, frozen Potato, new, stored, baked
F E
Spinach, frozen Sweet potato, baked Residue Carrot, cooked Corn, cooked Potato, new: stored, baked
F B
Turnip, cooked
B K E B
1'/2 to 101/2 9-11 yr. = 91 to 1 2 1 ; test yr. = 15 . O 4.0 15.0
2 3
F CEF
2 8
1 1
FK C
2
4 yr.
1 1
1
C K CEF
(1 1 (3)
1
C
= 190; test yr. = 0 to 3 , O ; test yr. = 0 9-11 yr. = 91 to 106; test yr. = 0 4 yr. = 130; test yr. = 0 "4
1
(12)
(1) -_ 13
Trithion (and methyl)
Systemics Dimethoate (.Ani. Cyan. 12880)
Bean, snap, canned Bean, Lima, canned Broccoli, frozen Cabbage, cooked Egg plant, cooked Peas, canned Potato, cooked Tomato juice, canned
F F F F F F F F
'/2
1.0 to 4 . 0
2 2 3 1 1 1 2
4.0
1
Bean, snap, canned Bean, Lima, canned Broccoli, frozen Peas, canned Potato, cooked
F F F F F
to 5.0 ' 1 2 to '/4 to '/4 to
1 . 0 to 2 . 0 23/4 and 5 . 0 1 . O to 7.0
11/2 41/a
'/a
2,o 1. o
1.o
4.0
2 1 1
1
1
FK FK F F F FK F F
5 3 5 1 1 2 3 1 21
FK FK FK FK F
11 2 6 4
5 28
Phosphamidon
Systox (demeton)
Bean, snap, canned Bean, Lima, canned Broccoli, frozen Cabbage, cooked Peas, canned Potato, cooked
F F F F F F
Bean, snap, canned Potato, new, baked
F E
1
FK FK FK F FK F
1 1
F E
2 1 1 1
1
"4
0.0312
10 4 4 1 2 3 24
2 2 4
18706 (.4m. Cyan.) Bean, snap, canned
F
1.0
1
FK
4
Location where grown. States or agencies responsible for results. A, Conn. Expt. Sta., New Haven. B, Entomology Research Div. or Crops Research Div., U.S.D.A. C, Human Nutrition Research Div., U.S.D.A. D, Mass. Expt. Sta. E, Maine Expt. Sta. F, Md. Expt. Sta. H, N. Y . Expt. Sta. M , R . I. Expt. Sta. Unless otherwise specified d Untreated except apples from Conn. and N. Y . , treated with pesticides previously shown not to affect flavor quality. Pounds or quarts/100 gal./ application. e Parentheses indicate results from residue study, not included in totals. a
b
218
AGRlCULTURAL A N D FOOD CHEMISTRY
Table II. Flavor Evaluations of Crops Treated with Single Fungicides
Fungicide
Producf
Bordeaux Captan (orthocide 50 or 80)
Potato, stored, baked .4pple, raw, stored 1 and 2l/2 mo. Stored 3l/2 mo.
Cop-o-zink Cuprocide Dichlone (phygon) Glyodin (Crag 341)
Potato, stored, baked Potato, stored, baked Potato, stored, baked Apple, raw, stored 1 and 2l/? .. mo . Stored 3l/2 mo.
Maneb (dithane M22, Potato, stored, baked manzate) PCNB (Terrachlor) Potato, stored, steamed
Locationalb
Pounds or Quarts 100 Gal./ApplicatianC
+ 4.0)
No. o f Crop Yr.
Tested byb
Flavor Compared to Standardd OffBetter Equal Poorer flavor Number of Tests
5 1
E
2.0
1
E
E E E E
4.0 2.0 1.0 1 0
1 1 I 1
E E E E
1 2 1 2
E
1 .O
1
E
-
E
E
(8.0 2.0
E
E E, No. Dak. E E E
5
E
1.0and2.0
2
E
50 lb./acre
1
CE
7
1
2 1
2 1
1 1
1 1 1
-
6
5
Tennan Potato, stored, baked 4.0 1 E 2 Tribasic copper Potato, stored, baked 4.0 5 E 5 8 Zineb (tank mixed) Potato, stored, baked (2.0 1.0) 5 E 4 9 a Location where grown. b States or agencies responsible for results. A, Conn. Expt. Sta., New Haven. B, Entomology Research Div. or Crops Research Div., U.S.D..4. C, Human Nutrition Research Div., U.S.D.A. D, Mass. Expt. Sta. E, Maine Expt. Sta. F, Md. Expt. Sta. H, N. Y . Expt. Sta. K,Pa. Expt. Sta. Unless otherwise specified. d Untreated except apples from Conn. and i T,Y. treated with pesticides previously shown not to affect flavor quality.
Table 111.
Pesticide"
+
Flavor Evaluations of Crops Treated with Multiple Pesticides
Producf
locotionhfe
-Pounds
or Q u a r i d 100 Gab/Application
No. of Crop Yr.
Testedc by
1 2 1
DEF DEF DEF
Flavor Commred f a Sfandardd OffBetter Equal Poorer flavor Number o f Tests
BHC
+
Cu Black Leaf 253 glyodin
Squash, canned Apple juice, frozen Applesauce, canned
+
3
2 3 -
5
3 3
DDT
+ captan
+
PbAs +captan Cypres dieldrin ferbam glyodin parathion S micronized thiram f thiram PbAs toxaphene
++ + + + + + + + +malathion toxaphene + Diazinon captan dieldrin ferbam glyodin Niacide M PbAs S micronized thiram
+ ++ + + ++
Dibrom Thiodan Dieldrin
+
+
1 2 1 1 1 2 1 1 1 2 2
F F
2 ,o-l'/p 2.0-2,0-11/? 2.0-'/2 21/2-0.19/ 2,0-1'/2 2.0-1'/? 3.0-3/~1 2.0-5.O 2,0-1'/2 2.0-2,0-1'/? 9yr. = 158 - lob;! test yr. = 20.0-15,OJ 1.0-1.Of 1.0-1,0-33/,f
1 1
FK
Apple, raw Spinach, frozen Apple, raw Apple, raw .4pple, raw, sauce
H F H H B
2,0-1'/2 2'/2-0.19/ 2,0-1'/2 2 ,o-1'/2 14.0-1.0-7.0
Apple, raw Apple, raw
H H
2,O-5. O 2,0-11/2
Apple, raw Apple, raw, cooked .4pple, raw Spinach, frozen Apple, raw Apple, raw Broccoli, frozen Apple, raw Apple, raw .4pple, raw, cooked Potato, baked
H
Spinach, frozen Spinach, frozen
Broccoli, frozen
F
H H H E,
F
1.0-3/~/
FK
FK FK FK FK FK F FK FK FK CE
2 7 2 1 2 4
1
1 2 2 4 1
2 1
FK
1 1
1 1
1 1 1 1 1
FK FK FK FK C
1 1 2 2 2
1 1
1 1
FK FK
2 -2 12
1
FK
-
2
2
2 (Continued on page 220)
V O L . 9, NO. 3, M A Y - J U N E
1961
219
Table 111.
Flavor Evaluations 04 Crops Treated with Multiple Pesticides (continued from page 219) Flavor Compared to Standardd Off-
No. of locaPesticide"
Product
++ DDT diazinon + malathion
Spinach, frozen Spinach, frozen Spinach, frozen
tionbjc
Pounds or Quartsd J 0 0 Gal./Applicafion
crop
Tesfed
by
Yr.
Beffer
-
FK FK FK
F F F
Equal Poorer Number o f Tests
1 1 _-2
4
Guthion captan ferbam glyodin S micronized thiram
+++ ++
Apple, Apple, Apple, Apple, Apple,
Lead arsenate DDT captan DDT thiram diazinon Niacide M malathion captan
++ + +
++ +
+
Malathion captan
+
+ captan + PbAs
++ dieldrin maneb
++ methoxychlor methoxychlor + captan f methoxychlor + captan + TDE + perthane ++ ryania ryania + captan + glyodin ++ Thiodan toxaphene ++ toxaphene toxaphene +
raw raw raw raw raw
1 1 1
1 1
2 2 2 1 _1 8
FK FK FK FK FK
1 1
2
1
-1
2
Apple, raw. cooked Apple, raw, cooked Apple, raw, sauce
H H B
2.0-2.0-11/2 2 0-2.0-1'/2 1 0-14.0-7.0
2 2 1
FK FK C
7 4 2
2
Applesauce, canned
A
3.0-2.0-2.0
1
DEF
3 16
-
Cantaloup. raw Squash, cooked, canned IVatermelon, raw Applesauce, canned Spinach, frozen Cantaloup. raw Squash, cooked IVatermelon, raw Apple juice, frozen Apple juice, frozen
D D D A F D D D A .4
5.0-9. Of 7.0-12. Of 7 0-12 01 2 0-3 0-2 0 6'/4-0 19f 5 0-10 Of 7,O-14. Of 7.0-14Of 2.0-3,0 2,0-3,0-2.0
Applesauce, canned
A
Broccoli, frozen Apple juice, frozen Applesauce, canned Broccoli, frozen Broccoli, frozen Spinach, frozen Spinach, frozen
D DEF
1 1
1 1 1 1 2
D D DEF DEF
1 3
2.0-1'/2-2.0-1'/2
1
DEF
3
F A A F F F F
8'/4-7,Of 2.0-6.0-2.0 2.0-6.0-1.0 11/~-3/2 25.0-3O.Of 6l/,-4.01 33/4-1,O-1. O f
1
F EF DEF
2
1 1 1 2 1
.Apple juice, frozen Apple juice, frozen
A .4
3.0-2.0 3.0-2.0-2.0
1 2
DEF DEF
3 5
Applesauce, canned
A
DEF
3
Squash, cooked Cucumber, raw Squash, cooked Watermelon, raw
D D D D
1 2 1 1
2
2
1
1 5
3
2
3
1
DDT
Methoxychlor malathion malathion captan malathion captan TDE maneb zineb
++ + ++
+
+ +
~
4.0-6.0 121/2-25.0f 7l/2-15.Of 10.0-2O.Of
D D D D
1 1
1
1
Parathion DDT Perthane malathion
+ +
Rotenone copper
+
+ maneb Ryania malathion captan malathion glyodin
+ +
220
+ +
1 1 13
Broccoli, frozen
F
'/4-3.O J
1
F
Broccoli, frozen
F
7.0-83/af
1
F
2
Cantaloup, raw Squash, cooked IVatermelon, raw Cantaloup, raw Squash, cooked IYatermelon, raw
D D D D D D
13/a-101/2/ 13/4-101/2/ 2.0-12. Of 1 3/4-14.Of 1'/2-12,0, 2.0-16.01
D D D D D D
2 1 2 1 1 _1 8
Apple juice, frozen
A
6.0-2.0-2.0
EF
Applesauce, canned
A
6.0-2.0-1.0
DEF
AGRICULTURAL A N D F O O D CHEMISTRY
3
1
~
4
1
1
-
1
2 3
flavor
1
Flavor Compared to Standardd
Pesticidea
Producl
Sevin captan Cyprex glyodin thiram
+ + ++
Apple, raw, cooked Apple, raw Apple, raw Apple, raw, cooked
Locafionb I C
H H H
H
Pounds or Quortsd 100 Ga/./Applicafion
2.0-2.0 2.0-1/2 2,0-11/2 2.0-1'/*
N o . of Crop Yr.
2 1 1 2
OffTested by
FK FK FK FK
Better
1
1
Equal Poorer flavor Number o f Tests -
5 2 1 4 12
3 2 5
TDE
+ malathion + methoxychlor captan
+
Thiodan Dibrom malathion
+ +
Toxaphene DDT
+
+malathion DDT +
+ malathion Fungicides Captan (orthocide 50 or 80) DDT DDT PbAs diazinon Guthion malathion
+ + + + +
+
+PbAs malathion + + malathion + methoxychlor + malathion + methoxychlor + TDE +ryania malathion + + Sevin
Applesauce, canned
A
Broccoli, frozen Broccoli, frozen
F F
Spinach, frozen Potato, baked
F E
Spinach, frozen
F
9 vr. = 106-158,; test yr. = 15-2Of 1 . O-1 . 0-33/af
Broccoli, frozen Spinach, frozen
F F
30.0-25.0/ 4,0-6'/,f
Apple, raw Apple, raw, cooked Apple, raw Apple, raw Cantaloup, raw Squash, canned, cooked IVatermelon, raw .4pplesauce, canned
D D D A
Apple juice
1'/*-2.0-1'/*-2,0
1.0-1, Of
1
DEF
1 1
FK FK
1 2
FK CE
1
FK
1
1
2 1
F FK
2 2 7
2 -
3
2
2 4 1 1
9.'d-5.07 12.0-7.0, 12 0-7.0, 2.0-3.0-2.0
1 2 1 1 1 2 1 1
FK FK FK FK D DEF D DEF
2 7 2 2 1 1
A
2.0-2.0-3.0
2
DEF
5
Applesauce
A
2 0-2.0-1'/2-1'/3
1
DEF
3
Apple juice
A
2.0-2.0-6.0
1
EF
2
Apple, raw, cooked
H
2.0-2.0
2
FK
+ +
Squash, canned IVatermelon, raw Cantaloup, raw Squash, cooked
Cyprex DDT Sevin
+ +
Apple, raw Apple, raw
H H
'/2-2.0 '/2-2.0
1 2 2 2
DEF D D D
1 1
FK FK
2
3
2
2
1
1
3
1
Copper BHC rotenone
1 1
5 33
3 2 2 1 __ 8
3
3 8
-
-
1
1 1
-
2 2 4
Ferbam DDT diazinon 4- Guthion
Apple, raw Apple, raw Apple, raw
Glyodin R1. Leaf 253 DDT diazinon Guthion malathion ryania Sevin
Applesauce, canned Apple, raw Apple: raw Apple, raw Applesauce
A H H H A
1 .0-2'/2 1'/',-2 0 , _
Apple, raw
Cantaloup, raw Squash, cooked TVatermelon. raw
+ +
+ + + + + +
Maneb malathion
+
+
1 1 1
FK FK FK
2 2 2 6
1'/?-2 . O 11/?-13/~ 1 .O-2.0-6.0
1 2 1 1 1
DEF FK FK FK DEF
3 4 2 2 3
H
1'/2-2 0
1
FK
D D D
10.0-5.01 14.0-7.0, 14.0-7.0,
1 1 1
D D D
~
~
1 1
-
1 15
. _ _ ~ ~
1
1 1 (Continued on p a g e 2 2 2 )
VOL. 9, NO. 3, M A Y - J U N E
1961
221
Table 111.
Flavor Evaluations of Crops Treated with Multiple Pesticides (continued from page 221) Flavor Compared to Standarde
locaPesticideu
Product
++ methoxychlor rotenone
Squash, cooked Cantaloup, raw Squash, cooked Watermelon, raw
tionb
D D D D
be
Pounds or Quartsd 100 Gal./Applicafion
6,O-4.Of 14.0-13/,t 1 2 , o-l'/2f
1 6.0-2.Of
Off-
No. o f Crop Yr.
Tested byC
1 1 1 1
D D D D
Fquol Poorer flovor __-Number of Tests Better
1
-
1
Niacide M diazinon PbAs Sulfur micronized DDT diazinon Guthion
+ ++ +
+
Thiram DDT DDT PbAs diazinon Guthion Sevin
+ ++ + +
+
1 1 1 -
5
Apple: raw, sauce
B
1.0-2.0-1.0
1
C
2
Apple, raw Apple, raw Apple, raw
H H H
5,0-2.O 5.0-2.0 5 , 0-131a
1 1 1
FK FK FK
2 2
Apple, Apple, Apple, Apple, Apple, Apple,
raw raw, cooked raw raw raw, cooked raw
H H H H H H
1 2 1 1 1 1
1'/9-2,0
FK FK FK FK FK FK
+ +
(tank mixed) tribasic Cu
+
+ 1.0)
Potato, stored, baked
E
4.0-(2.0
Cucumber. raw Squash, cooked iyatermelon, raw
D D D
25.0-12'/if 15 .0-71/~f 20.0-10.01
Potato. stored, baked
E
(2.0
+ 1.0)-4.0
1
E
1 1 1
D D D
1
E
1
1 5
1 -
2 4 2 1
2
1
1
4 -
13
Tribasic Cu zineb Zineb methoxychlor
-
1
2 5
1 1 1 1
1 1
-
1 3
1
Pesticides cross-indexed. Location where grown. States or agencies responsible for results. A, Conn. Expt. Sta., Xew Haven. B, Entomology Research Div. or Crops Research Div., U.S.D.A. C, Human Nutrition Research Div., U.S.D.A. D, Mass. Expt. Sta. E, Maine Expt. Sta. F, Md. Expt. Sta. H, N. Y . Expt. Sta. K, Pa. Expt. Sta. d Unless otherwise specified. 8 Untreated except apples from Conn. and N. Y . , treated with pesticides previously shown not to affect flavor quality. 1 Total actual pounds per acre. 5
c
i.e., application to the crop of two or more insecticides, fungicides, or a combination of the two. Pesticides in Table I11 are cross-indexed to make the information useful to both pathologists and entomologists, even though this involves repetition of the data. O n some pesticides, relatively few observations were made. A few of these involved new and or experimental materials. Others were discarded after brief testing because of discontinuance of the use of the pesticide, the introduction of new and more effective materials to supersede the old, or limited applicability. I t was decided to release all of the findings for the benefit of the users and manufacturers of the materials as well as to stimulate other investigators to fill the gaps where more data are needed. The data reported here were combined from all cooperating laboratories. They were verified independently by each investigator, who interpreted his own results. The tables include some information on the actual amounts of pesticidal materials applied. For sprays. this is presented as pounds or quarts per 100 gallons
222
per application as necessary in area of production. The pesticides in dust form are recorded as total pounds of actual ingredient per acre for soil or foliar applications or a combination of the two. .4n insecticide applied a t 1 pound per acre nine times is recorded as 9 pounds. I n a few experiments. excessive dosages were applied to simulate careless use of pesticides or to telescope the effect of long-term ap20 pounds per acre plications-e.g.. of chlordan or 15 pounds per acre of toxaphene per year for several years. Possible relevant details as to dates of application, nearness to harvest. depth and distribution of soil-applied chemicals, soil type, etc., are omitted. The locations of the field trials are labeled, and the reader may obtain the treatment schedules in greater detail from these sources. Fifteen of the 36 single insecticides were represented by 14 to 68 evaluations and seven of the 17 combined insecticides by 14 to 45 tests. Fungicides were not so widely tested. Three of the 11 single fungicides wcre tested 13 times and three of 11 combinations were eval-
AGRICULTURAL A N D FOOD CHEMISTRY
uated 16 to 43 times. Many of the data have been or will be published in greater detail as separate studies. Average scores of treated samples showing "slight off-flavor" were infrequent and "definite off-flavor" average scores were rare enough to be ignored, Both off-flavor categories are tabulated and discussed together. Discussion is generally limited to those pesticides or combinations of pesticides on which a sufficient number of evaluations were made to give some conception of distribution.
Discussion .4bout 21, lo! and 2OY0 of the samples treated with BHC, lindane, and toxaphene, respectively, were judged to be off-flavor. The multiple pesticide treatments including toxaphene were judged off-flavor in 147, of the samples. Five single insecticides indicated a noteworthy degree of adverse effect on flavor quality (significantly "poorer than standard" plus off-flavor). BHC, lindane, and toxaphene treatments in-
duced poor flavor quality in 57, 55, and 48% of 1.4, 20, and 25 samples, respectively. T h e high level of ill effects from toxaphene was mainly for potato samples grown on soil treated with 15 pounds per acre applied in alternate years for 9 to 11 years as well as in the test year, a relatively high dosage (probably three to five times the amount necessary for insect control). Twenty-five per cent of the 24 samples treated with endrin and 16% of the 68 samples treated with malathion were judged to be in the poorer flavor category. Single insecticides which in general did not induce poor flavor quality as based on 14 or more evaluations were: chlordan, D D T , Dibrom, Dilan, dimethoate, heptachlor, phosphamidon, Sevin, Thiodan, and Trithion. Improved flavor quality was observed in 10 to 13% of the samples treated with chlordan, heptachlor, lindane, and endrin. Two of these-lindane and endrin-also showed a n appreciable degree of poorer flavor. Samples treated with toxaphene in combination with other insecticides had poor flavor quality in 50% of 14 tests, reflecting the results with potatoes (three of seven poor samples). About 28YG of 18 samples treated with Sevin in combination with other pesticides were evaluated as poorer than standard, seemingly because of the interaction of pesticides. Samples treated with the combination of D D T with other pesticides showed quality loss in 2470 of 38 samples, demonstrating the influence of toxaphene (five of nine poor samples). T h e single effect of Sevin and D D T was negative. hlaiathion in combination induced adverst: flavor effects in 2770 of 45 samples as compared with its single influence on 16f:b of 68 samples. Three of the: 11 single fungicidesBordeaux, tribasic copper, and zineb, with 13 tests each on potatoes onlysho\ved no ill effects on flavor and induced better flavor quality in approximately one third of the 13 tests. Although the PCNB treatments involved potatoes only in one crop year? in 11 tests (by tkvo laboratories on tivo varieties from S o r t h Dakota and one from Maine) five of the samples were judged off-flavor and the other six poorer than standard. None of the fungicides in combination resulted in mean scores showing slight or definite off-flavor. Poorer samples were evident, Iioivever~ in nine of 43 (21y0) captan-1-reated, and five of 18 (287,) thiram-treated samples. Of these 14 poorer samples, six were in combination with malathion and five others involved Sevin.
With multiple pesticides, it is difficult to ascribe poor flavor quality to a single component of the treatment, and the possibility of interaction should not be ignored. There was no evidence of improved flavor quality associated with multiple treatments. I n the data shown some contradictory results are noted, in that the use of certain pesticides resulted in better as well as poorer flavor. These aberrant situations may be related to specific crop response, to soil type, to crop years with their varying macro- or micro-climate, to pesticidal carriers. to method, time, and distribution of the pesticides, or to unknown factors. T h e data presented from the NE-15 long-term study admirably demonstrate the need for continued and multiple observations before dogmatic interpretations may be made. New Jersey was a member of the NE15 project for three years with emphasis on instrumentation. T h e New Jersey Food Technology Department pursued taste panel evaluations on samples grown, treated, and tested in New Jersey. More ill effects were evident in the New Jersey tests than among all of the others-e.g., aldrin, chlordan, and dieldrin were classified as poorer than standard (7). T h e Yew Jersey results were omitted from the tables and the general discussion because they did not represent the group findings and because no samples were exchanged with other members. T h e validity of the New Jersey tests is recognized, and it is deemed that neither methodology nor panel acuity is responsible for the lack of agreement. Possible factors which may be related to the discrepancy between the S e w Jersey and the other samples are soil type. product form. formualtion of the pesticides. and other extraneous influences as discussed above. T h e NE-15 study \vas not designed to examine these possible interacting agents and any a posterion conclusions Ivould be of dubious validitv. Conclusions
Coordinated through the %E-I 5 regional project, seven state experiment Stations and the U. S. Department of Agriculture examined by organoleptic methods crops treated with pesticides to determine their influence on flavor quality. During six years, 528 evaluations on 36 single insecticides, 152 on 18 combinations of insecticides, 66 on 11 single fungicides, and 118 on 11 fungicide combinations were made. Each average score represented the opinion of a
trained or experienced panel ranging from five to 40 members and was based on a minimum of 20 judgments. Insecticide evaluations involved 23 crops (20 vegetables and three fruits). Fungicide treatments were used on six crops (five vegetables and one fruit). Five of the single insecticides and one of the single fungicides were associated with a notable degree of poor flavor quality. Six combinations of pesticides had adverse effects on flavor. Some of these seemed to be related to specific components of the multiple treatments while others were ascribed to interaction. The committee does not condemn nor endorse any particular pesticide or combination of pesticides. Both known and unknown influences may alter the picture and vitiate any blanket conclusions. \Ve suggest rather that these data be considered a reference summary for the reader to consult according to his own interest as to crop, amount of pesticide, number of crop years tested, and degree of accord among analysts.
Acknowledgment
Persons responsible for furnishing uniform samples to the laboratories Ivere: entomologists: L. P. Ditman, University of Maryland; Phillip Garman, Connecticut Experiment Station; C. H. Hoffman, Entomology Research Division, U. S . Department of Agriculture; G. \V. Simpson, University of Maine; and W. D . TVhitcomb, Massachusetts Agricultural Experiment Station. Pathologists: Reiner Bonde, L n iversity of Maine; F. L. Howard, U n iversity of Rhode Island; and D. H. Palmiter, New York Experiment Station. Horticulturist: V. R. Boswell, Crops Research Division. U. S. Department of Agriculture. Gratitude is accorded to the many conscientious panel members and laboratory assistants and to the several entomologists and pathologists who are not specifically credited.
Literature Cited
(1) Stier, E. F., personal communication, 1960. (2) \Viley, R. C., Briant, A. M., Fagerson, I. S., Murphy, E. F Sabry, J. H., Food Research 22, 192-2;s (1957). (3) Wiley, R. C., Briant, A. M., Fagerson, I. S.,Murphy, E. F., Sabry, J. H., Food Technol. 11, 43-8 (1957).
Received for review August 78, 7960. Accepted December 72, 1960.
VOL. 9, NO. 3, M A Y - J U N E
1961
223
